RI 6186 Recovery Of Low-Silica Cryolite From Siliceous Fluoride Offgases

This work was conducted to determine a feasible process for converting siliceous fluoride offgases to a commercially usable product. The offgases were generated by pyrohydrolytic defluorination of low-grade fluorspar in a gas-fired rotary kiln, and fluorine was collected as a hydrofluoric-fluosilicic acid. A silicon-free fluoride solution for further processing was then produced by neutralizing the acidic scrubber solution with anhydrous ammonia, silicon being separated as orthosilicic acid. Ninety to ninety-nine percent of the fluorine originally present remained in solution as ammonium fluoride. Silicon was also separated from synthetic fluosilicic acids, having F-to-Si weight ratios ranging from 3.50 to 14.3. The solutions below a ratio of 4.06, the F-to-Si ratio of H2SiF6, containing dissolved silicon were desiliconized as completely as those containing less than the stoichiometric quantity of silicon. An electrolytic-grade cryolite was recovered from the ammonium fluoride solution by reacting with either sodium aluminate or alumina trihydrate and sodium hydroxide. A product containing 97 to 100 percent of the fluorine, represented by Na3A1F6, was recovered, and 94 to 99 percent of the theoretical yield was realized.